Use of molar mass controlled cellulose

ABSTRACT

According to an example aspect of the present invention, there is provided a use of molar mass controlled cellulose in injection molding, extrusion and three dimensional printing applications.

FIELD

The present invention relates to novel biodegradable thermoplasticmaterials made from molar mass controlled cellulose and to novel usesthereof. These materials are easily processable by existing filmextrusion, injection moulding and three dimensional printingmachineries.

BACKGROUND

Cellulose is the most abundant renewable organic polymer on the earthand hence can be regarded as important raw material for severalindustries such as textiles, papers, foods, cosmetics and biomaterials(Edgar et al., 2001). Cellulose is a linear polymer that consists ofβ(1→4) linked D-glucose units. Hydroxyl groups of cellulose forms stronginter and intra molecular hydrogen bonds and van der Waals interactionsforming a resistant and stiff microfibril network. This structure is notuniform, and both highly ordered (crystalline) regions and regions witha low degree of order can be found. The relative proportion of theseregions depends on the raw material and the treatments to which thecellulose has been produced (Klemm et al., 2002). Moreover, theseregions caused the limited solubility of cellulose and make it difficultfor solvents and reagents to access areas within the cellulose fibres.As known this network is poorly reactive requiring a large excess ofchemicals or demanding process conditions.

The modification of cellulose can be done either via homogeneous orheterogeneous procedures. In most cases, cellulose esters are producedindustrially under heterogeneous conditions. Reaction rates and finaldegree of substitution (DS) in heterogeneous reactions are hindered bylow accessibility of solid cellulose to the esterification reagents (Weiet al., 2007). In order to have homogeneous chemical reaction celluloseneed to be first dissolved. In order to achieve uniform chemicalreactions or solubilization of cellulosic substrates, it is important tohave accessibility high enough. However, due to the high crystallinity,cellulose can be only dissolved in limited solvents at lowconcentrations. To achieve chemical reactions efficient enough, thenative cellulose need to be first activated by disrupting inter- andintramolecular hydrogen bonding making structure accessible to furtheraction of reactants. This can be achieved by varying degrees ofchemical, enzymatic or mechanical activation.

The chemical activation can be achieved by different methods like usingwater, solvents, dilute acids and bases. As a result of chemicalactivation the cellulose structure becomes less ordered leading to anincrease of the active surface area and thus increasing the number ofavailable hydroxyl groups and the accessibility to chemicals. Well knownmethod to disrupt fibrillar aggregation, and increase surfaceaccessibility is to use fluids with a higher swelling power, such asdilute caustic soda (6-10%), dilute quaternary bases or aqueous zincchloride. Disruption of the crystalline structure, such as with liquidammonia or 20% caustic soda, which induces cellulose-I to cellulose-II(also regenerated cellulose) crystal modification. Treatments by acidhydrolysis and oxidation, thermal and mechanical treatments by grinding,ultrasonic treatment and freeze-drying and enzymatic treatment are alsoactivation methods but they can degrade the molecules to a certainextent.

The enzymatic activation of cellulose can be done by using differentcellulases which hydrolyse the 1,4-β-D-glucosidic bonds of the cellulosechain. There are three major groups of cellulases: endoglucanases,cellobiohydrolases or exoglucanases, and glucosidases. These enzymes canact alone on the cellulose chain or together degrading efficientlycellulose structure generating mainly glucose or cellobiose units.

The mechanical activation of the cellulose fibres is well known methodin the pulp and paper industry. Depending on how and in which conditionsthe mechanical processing has done it can enhance fiber-fiber bonding,to cut or make the fibres stronger and to change cellulose structure.

Crepy et al. (2009) describe a method for synthesizing plastic materialsby the internal plasticization of cellulose with fatty acids.Modifications were done in homogenous solvent under microwaveirradiation, which is not currently industrially feasible. The methoddoes not cover both homogeneous and heterogeneous reactions for molarmass controlled hydrolyzed cellulose.

For the application point of view cellulose solubility and mechanicalproperties need to be tailor without affecting its natural performancetoo much. For instance, to avoid tedious recycling processes of solventsand huge excess of chemicals in chemical activation cellulose reactivityneed to be increase without losing its good mechanical properties toobtain high quality cellulose based materials which are suitable forvarious applications. One way to increase reactivity of the cellulose isto decrease its molar mass in controlled manner.

WO 2016/193542 discloses a method of improving the reactivity ofcellulose in order to utilize cheap and easily available raw materialand obtain excellent performance for biomaterial manufacturing, whichmakes it a suitable starting point for the present invention. Thepublication does not however disclose use of a molar mass controlledthermoplastic material in injection moulding, film extrusion and threedimensional (3D)-printing for obtaining recyclable and biodegradableobjects.

SUMMARY OF THE INVENTION

The invention is defined by the features of the independent claims. Somespecific embodiments are defined in the dependent claims.

According to a first aspect of the present invention, there is provideda use of a cheap and available raw material for biomaterialmanufacturing.

According to a second aspect of the present invention, there is provideda use of hydrolyzed and reactive molar mass controlled cellulose, havingfor example excellent thermoplastic properties.

These and other aspects, together with the advantages thereof over knownsolutions are achieved by the present invention, as hereinafterdescribed and claimed.

The use of the molar mass controlled cellulose is mainly characterizedby what is stated in the characterizing part of claim 1.

Considerable advantages are obtained by means of the invention. Forexample, the modification of hydrolyzed cellulose as herein describedprovides easily processable thermoplastic materials without using anyexternal plasticizers. Additionally, this material is cheap and easilyavailable, provides excellent performance and is processable by usingexisting process machines. Furthermore, the material and productsobtained thereof are biodegradable and recyclable as being fullybio-based.

Next, the present technology will be described more closely withreference to certain embodiments.

EMBODIMENTS

The present technology provides means to convert inactive cellulose tomore reactive form and to an easier functionalization in order toproduce thermoprocessable cellulose products by means of for exampleinjection moulding, film extrusion and three dimensional printing.

“Long-chain fatty acid modification” herein means chain length of fattyacid substituents ≥C6, such as C6-C30 and more preferably C6-C18. Suchmodification may for example be esterification or etherification.

FIG. 1 is a photo describing the molar mass controlled cellulosematerial of the present invention in form of granules.

FIG. 2 is a photo describing the molar mass controlled cellulosematerial of the present invention processed by three dimensionalprinting.

FIG. 3 is a photo describing the molar mass controlled cellulosematerial of the present invention processed by film extrusion.

FIG. 4 is a photo describing the molar mass controlled cellulosematerial of the present invention processed by injection moulding.

One aspect of the present invention is a method of improving thereactivity of cellulose and preparing a transportable form of theprevious for preparation of thermoplastic, dispersion able or dissolvingderivatives, wherein molar mass and molar mass distribution of thecellulose is controlled uniformly to a range between 30 and 300 kDatherefore providing reactive and processable cellulose.

The method of improving the reactivity of cellulose comprisescontrolling (i.e. decreasing) the molar mass of a cellulose raw materialvia hydrolysis, excluding total hydrolysis, and by performing along-chain (chain length between C6 and C30, such as C6-C18) fatty acidmodification for the molar mass controlled cellulose.

The method comprises controlling (i.e. decreasing) the molar mass of acellulose raw material via hydrolysis, excluding total hydrolysis, andby performing a hydroxyalkylation modification, e.g. hydroxypropylation,hydroxyethylation or hydroxybutylation for the molar mass controlledcellulose.

The hydrolysis is controlled so that the average molecular mass of thecellulose is reduced at least 40% but not more than 85% from themolecular mass of the starting raw material. It is preferred that thehydrolysis is controlled so that after the hydrolysis the averagemolecular mass of the cellulose is between 30 to 300 kDa, preferablybetween 40 to 200 kDa. It should be noted that the molar mass of thecellulose is indeed controlled, whereby the cellulose is not subjectedto total hydrolysis.

As an example, the inventors prepared cellulose palmitates byheterogeneous esterification in pyridine and homogeneous esterificationin the solvent of DMAc/LiCl. To see difference in reactivity,esterification was tested for both native softwood sulfite pulp andmolar mass controlled cellulose. In addition, not only to focuscellulose reactivity, the inventors also tested these derivatives aspotential thermoplastic materials as well in applications where good andstable water vapor barrier properties are needed. It is described hereinhow the cellulose raw material molar mass has significant effect tocellulose reactivity. Using hydrolyzed cellulose as a starting material,better reaction efficiency was obtained without losing the goodproperties of the cellulose esters.

As another example, commercial softwood sulphite dissolving grade pulpwas treated with ozone to decrease the degree of polymerization. Afterthe ozone treatment the pulp was subjected to hydrogen peroxidetreatment aiming to further decrease the degree of polymerization and toreduce the content of carbonyl groups of the pulp.

The cellulose raw material is selected from native softwood pulp, nativehardwood pulp, annual plant pulps such as bamboo pulp or straw pulp,softwood sulphite dissolving grade pulp, hardwood sulphite dissolvinggrade pulp, ozone treated hydrolyzed pulp or enzyme treated pulp.

Thus, the cellulose material is hydrolyzed and activated by enzymatictreatment, ozone treatment, hydrogen peroxide treatment, alkalinetreatment, or other chemical treatment, before performing a long chainfatty acid modification, such as an esterification or hydroxyalkylation.

The long-chain fatty acid modification comprises either heterogeneousesterification or homogeneous esterification of the cellulose.

In case of homogenous esterification, the cellulose raw material isfirst dissolved into LiCl/DMAc solution.

The long chain fatty acid modification comprises heterogeneousetherification of the molar mass controlled cellulose, for example byhydroxyalkylation. The hydroxyalkylation reaction of the activatedcellulose was herein subjected in alkaline conditions either with orwithout inert solvent such as toluene.

The target substitution level can be adjusted based on reactionconditions such as the amount of reagents and reaction time. The purityof washed esters was confirmed by FT-IR and NMR analysis to verify thatall unreacted propylene oxide had been removed.

The target degree of substitution for the cellulose esters was found tobe (DS>0.7) for both heterogeneous esterification and homogeneousesterification in the solvent of DMAc/LiCl. DMAc/LiCl-system can be usedto dissolve cellulose without any degradation of cellulose. The purityof washed esters was confirmed by FT-IR and NMR analysis to verify thatall unreacted fatty acid had been removed.

Thus, a cellulose ester and a cellulose ether obtained by the method asherein described has chain length between C2 and C30, such as C6-C18,and has a total degree of substitution (DS) from 0.7 to 3.

According to DS values of synthesized cellulose palmitate, it can beconcluded that the molar mass of starting material has a significanteffect to the end product degree of substitution. Both in homogeneousand heterogeneous method, DS values increased when molar massesdecreased when similar reaction conditions were used. When pulps wereused in homogeneous system, degrees of substitution were >0.7 and theformed cellulose esters were fully soluble to chloroform. In that casefilms could be prepared for example by simple solvent-casting and/orextrusion and these films have high flexibility and opticaltransparency. Cellulose esters, which were synthesized in heterogeneoussystem using hydrolysed cellulose pulp showed also high DS andtransparent films could be obtained. However, in that case, thecellulose esters were not fully soluble to chloroform due the unevendistribution of such as palmitate functionalization and therefore someinsoluble cellulose fibrils were observed.

A method of producing thermoformable cellulose ester or ether films ischaracterized by preparing the films from the purified cellulose estersor ethers without using any external plasticizers. However, plasticizersmay be used for optimization causes.

One embodiment of the present invention is a use of bio-based andbiodegradable thermoplastic material, wherein the material is molar masscontrolled cellulose ranging between 30 and 300 kDa, in injectionmoulding, film extrusion and three-dimensional printing without anyexternal plasticizer.

Another embodiment of the present invention is that the molar masscontrolled cellulose material is manufactured into form of granules andprocessed as such. Known bio-based thermoplastic materials cannot beformulated into granules, but instead are produced as flakes. Thisfeature of granule form makes the transportation and adaptation of theraw material into the process cheaper and easier. Herein, a granule or agranulate or similar is a free-flowing particle having a diameter of 0.5to 4 mm.

According to one embodiment of the present invention, temperatures suchas below 160° C., preferably between 110 and 150° C., can be used ininjection moulding and film extrusion applications. These temperaturesare essentially lower than in conventional processes, because of lowerthermo-mechanical stress. Also, these temperatures are readilyapplicable to existing process machines. Furthermore, lower temperaturesin the plasticizing stage prevent darkening of the material, which is aconventional problem in the art.

Further embodiment of the present invention is that that molar masscontrolled cellulose material is reprocessable at least two times,preferably at least three times. This means that the fatty acid workingas the inner plasticizer in the polymer chain does not break off whenmelting the material, because the process temperatures are low and theprocess does not require high mechanical force.

According to one embodiment of the present invention the used molar masscontrolled cellulose materials and the materials and/or objects producedthereof are compostable and/or recyclable.

According to a further embodiment of the present invention, the materialused is molar mass controlled cellulose palmitate.

It is to be understood that the embodiments of the invention disclosedare not limited to the particular structures, process steps, ormaterials disclosed herein, but are extended to equivalents thereof aswould be recognized by those ordinarily skilled in the relevant arts. Itshould also be understood that terminology employed herein is used forthe purpose of describing particular embodiments only and is notintended to be limiting.

Reference throughout this specification to one embodiment or anembodiment means that a particular feature, structure, or characteristicdescribed in connection with the embodiment is included in at least oneembodiment of the present invention. Thus, appearances of the phrases“in one embodiment” or “in an embodiment” in various places throughoutthis specification are not necessarily all referring to the sameembodiment. Where reference is made to a numerical value using a termsuch as, for example, about or substantially, the exact numerical valueis also disclosed.

As used herein, a plurality of items, structural elements, compositionalelements, and/or materials may be presented in a common list forconvenience. However, these lists should be construed as though eachmember of the list is individually identified as a separate and uniquemember. Thus, no individual member of such list should be construed as ade facto equivalent of any other member of the same list solely based ontheir presentation in a common group without indications to thecontrary. In addition, various embodiments and example of the presentinvention may be referred to herein along with alternatives for thevarious components thereof. It is understood that such embodiments,examples, and alternatives are not to be construed as de factoequivalents of one another, but are to be considered as separate andautonomous representations of the present invention.

Furthermore, the described features, structures, or characteristics maybe combined in any suitable manner in one or more embodiments. In thefollowing description, numerous specific details are provided, such asexamples of lengths, widths, shapes, etc., to provide a thoroughunderstanding of embodiments of the invention. One skilled in therelevant art will recognize, however, that the invention can bepracticed without one or more of the specific details, or with othermethods, components, materials, etc. In other instances, well-knownstructures, materials, or operations are not shown or described indetail to avoid obscuring aspects of the invention.

While the forgoing examples are illustrative of the principles of thepresent invention in one or more particular applications, it will beapparent to those of ordinary skill in the art that numerousmodifications in form, usage and details of implementation can be madewithout the exercise of inventive faculty, and without departing fromthe principles and concepts of the invention. Accordingly, it is notintended that the invention be limited, except as by the claims setforth below.

The verbs “to comprise” and “to include” are used in this document asopen limitations that neither exclude nor require the existence of alsoun-recited features. The features recited in depending claims aremutually freely combinable unless otherwise explicitly stated.Furthermore, it is to be understood that the use of “a” or “an”, thatis, a singular form, throughout this document does not exclude aplurality.

INDUSTRIAL APPLICABILITY

At least some embodiments of the present invention find industrialapplication in thermoplastic biomaterial manufacturing by moulding,extrusion and three dimensional printing. Furthermore, the presentinvention may be used in injection moulding, film extrusion, compositemanufacturing and heat-sealable packaging applications. Thesethermoplastic materials are fully bio-based, biodegradable, compostableand recyclable, and can be processed several times without highthermos-mechanic stress, i.e. high process temperature and highmechanical treatment forces.

Example 1—Synthesis of Molar Mass Controlled Cellulose Ozone Treatment

Z-stage was performed in a plastic flow through-reactor in mediumconsistency. Pulp was added into the reactor, and water was charged andthe pulp was mixed when the water addition was done. Initial pH wasadjusted with H₂SO₄ and oxygen flow through the reactor was started.

After 10 minutes ozone generator was started (160 A). Ozone generation(about 192 mg/min) in the carrier oxygen gas was first stabilized for 5minutes. After stabilization ozone flow was lead to the potassium iodidesolution (10 min), and after that gas flow was lead into the reactor.Pulp was mixed all the time during the ozone charging. Mixing wasstarted already one minute before the charging and continued for oneminute after the charging was finished. Ozone flow was lead again intopotassium iodide solution (10 min), and pulp was rinsed with oxygen flow10 minutes after the reaction time. Ozone formation was determined frompotassium iodide solution by titration with Na₂S₂O₃.

Hydrogen Peroxide Treatment

P-stage was performed in Teflon coated medium consistency reactor.Preheated pulp was added into the reactor, and after that, reagents werecharged, suspension was mixed and initial pH was measured. Mixing speedwas 210 r/min. After reaction time pH was measured from the pulp in thereaction temperature, and residual hydrogen peroxide content of thefiltrate was determined.

Pulp Washing

Washing between stages was a standard laboratory washing: Pulp wasdiluted to 5% consistency with deionized water, which temperature wasthe same as that of the preceding bleaching stage. After dewatering, thepulp was washed two times with cold deionized water with amountequivalent to ten times the absolutely dry pulp amount.

The intrinsic viscosity of the pulp was determined by a standard ISO5351-1. The viscosity test is a means for determining the extent ofcellulose degradation produced by cooking and bleaching. The limitingviscosity number of cellulose is determined in dilutecupri-ethylene-diamine (CED) solution. First the pulp sample iscontinuously shaken in flask containing deionized water and copperpieces until the sample has been completely disintegrated. Then the CEDsolution is added and shaking is continued until the sample has beendissolved. After this the efflux time of the sample is determined withviscometer. The measurement programme of the viscometer givesautomatically the intrinsic viscosity value of the sample.

Dissolving Cellulose to DMAc/LiCl System

Cellulose was dissolved by a method described by Sjöholm et al 2000.Cellulose (2-5 wt-%) was added via solvent-exchange (water/methanol/DMAcsequence) to 5% LiCl/DMAc solution. The mixture was heated to 80° C. for2 hours and allowed to slowly cool to room temperature. A uniformlytransparent cellulose solution was observed.

Preparation of Cellulose Palmitate Using Homogenous Method

The homogenous esterifications of the cellulose were conducted by usinga method, in which cellulose was first dissolved via solvent-exchange toDMAc/5% LiCl solution. Then anhydrous pyridine (3.6 equivalents tocellulose AGU) was mixed with cellulose solution. Finally palmitoylchloride (3.0 equivalents to cellulose AGU) was added slowly to thecellulose mixture. The mixture was then warmed to 60° C. and mixing wascontinued for 16 h at a constant temperature. The product was thenprecipitated with ethanol, filtered and additionally washed with ethanoland acetone.

Preparation of Cellulose Palmitate Using Heterogenous Method

Cellulose and anhydrous pyridine (20 equivalents to cellulose AGU) weremixed together and palmitoyl chloride (3 equivalents to cellulose AGU)was added slowly to the cellulose mixture. The mixture was stirredeither overnight at 60° C. or 5 h at 100° C. temperature. The productwas then precipitated using ethanol, filtered and additional washed withethanol and with acetone.

Example 2—Properties of the Molar Mass Controlled Cellulose

Mechanical properties were tested according to table 1, which also showscorresponding values for typical reference materials.

TABLE 1 Mechanical properties MMCC MMCC pilot 1 + Ref. Ref. Ref. Ref.Tests pilot 1 10% fiber PLA HDPE LDPE CA Tensile strength (MPa) 11 950-55 20-40  8-12 30-40 Young's modulus (MPa) 232 328 3500  200-1000200-400 1600 Elongation at break (%) 12 8  5-100 >100 >100 2-5 ImpactStrength (kJ/m²) 6.8 7 3-7  2-12 No break HDT 1.80 MPa (° C.) 33 3340-45 60 35-37 48-60 MFI (g/10 min) 3.2 2-5 4-8 1-4 Density (g/cm³) ~1~1 ~1.2 ~1 ~0.9 ~1.3 Melting temperature 130-150 120-170 120-190 120-160210 (° C.)

Thermal properties of samples were analyzed by differential scanningcalorimetry (DSC) (table 2). Because the long chain cellulose esters areamorphous, primary cellulose melting cannot be observed. In case ofcellulose palmitate, the detected melting is due to melting of theside-chains (FIG. 5). The side-chain melting can take place whencellulose ester substituent length is C10 or longer. Thus, no side-chainmelting can be detected for cellulose octanate. In case of C8/C16blends, the melting temperature (T_(m)) of C16 side-chain is almostconstant (27° C.), but the melting enthalpy decreases when the amount ofcellulose octanate is increased.

Either cellulose palmitate or cellulose octanate have no clear glasstransition temperature (T_(g)). Glass transition of PLA is 62° C. and itcan be detected, when samples contain 50 w % or more of PLA. Nosignificant change of PLA T_(g) was observed in the blends, but theenthalpy of T_(g) decreased when ratio of PLA in samples decreased.Multiple endothermic peaks corresponding to the melting of the PLAcrystallites (T_(m)) can be identified at around 150° C. for all PLAblends.

When cellulose palmitate is compounded with PLA, both the melting of PLAand the melting of cellulose palmitate side-chains can be detected, andthe melting enthalpies correlate well with the ratios in blends. Thesame behavior was observed in the case of C16/bio-PE blends. Glasstransition temperature of PE is lower than the minimum temperature (−40°C.) of the DSC analysis, so it cannot be observed due to the temperaturerange limitations of test equipment.

TABLE 2 Thermal properties of compounded samples Melting ΔCp T_(m)enthalpy T_(g) (J g⁻¹ Entry Material (° C.)^(a) (J/g)^(b) (° C.)^(a)K⁻¹)^(b) 1 C16 100%   27^(c)  30^(c) n.d n.d 2 C8 100% n.d n.d n.d n.d 3PLA 100% 151 27 62 0.25 4 PE 100% 132 176  n.d n.d 5 C16 75%:C8 25%  23^(c)  19^(c) n.d n.d 6 C16 50%:C8 50%   22^(c)   8^(c) n.d n.d 7 C1625%:C8 75%   21^(c)   5^(c) n.d n.d 8 C16 75%:PLA 25% 26^(c)/14917^(c)/9  n.d n.d 9 C16 50%:PLA 50% 25^(c)/149 11^(c)/14 60 0.07 10 C1625%:PLA 75% 25^(c)/150  5^(c)/23 62 0.14 11 C8 75%:PLA 25% 148  6 n.dn.d 12 C8 50%:PLA 50% 150 13 62 0.25 13 C8 25%:PLA 75% 151 22 62 0.22 14C16 75%:PE 25% 26^(c)/131 11^(c)/36 n.d n.d 15 C16 50%:PE 50% 25^(c)/131 6^(c)/92 n.d n.d 16 C16 25%:PE 75% 24^(c)/133  3^(c)/131 n.d n.d 17 C875%:PE 25% 133 40 n.d n.d 18 C8 50%:PE 50% 133 85 n.d n.d 19 C8 25%:PE75% 133 122  n.d n.d n.d = not detected ^(a)standard deviation ±2° C.(DIN 53765) ^(b)standard deviation ±7.5% (DIN 53765) ^(c)side-chainmelting temperature of cellulose palmitate

Reprocessability test was conducted with RAY-RAN Melt flow indexer(Model 3A) with load of 2.16 kg and melting temperature of 150° C.During first heating the melt flow index was 3.22 g/10 minutes andduring second heating the melt flow index was 5.04 g/10 minutes.

The result shows that the material is recyclable (without plasticizersand stabilizers) at least once, which is streamlined with the currentindustrial practices in the recycling systems in OECD countries.

CITATION LIST Patent Literature

-   1. WO 2016/193542 A1

Non-Patent Literature

-   1. Edgar K., Buchanan C., Debenham J., Rundquist. P, Seiler B.,    Shelton M., Tindall S., Prog. Polym. Sci. 2001, 26:1605-1688.-   2. Klemm D., Schmauder H.-P., Heinze T., Cellulose,    Biopolymers, 2002. 6: p. 275-319.-   3. Wei Y., Cheng F., Hou G., J. Sci. Ind. Res. 2007, 66: 1019-1024.-   4. Crepy L., Chaveriat L., Banoub J., Martin P., Joly N.,    ChemSusChem, 2009, 2(2), pp. 165-170.-   5. Sjöholm E., Gustafsson K., Erikssin B., Brown W.,    Colmsjo A. (2000) Aggregation of cellulose in lithium    chloride/N,N-dimethylacetamide, Polymers 41:153-161-   6. Hamod H., Degree Thesis: Plastics Technology, 2014, Arcada    University of Applied Science, Finland.-   7. http://www.matweb.com/reference/deflection-temperature.aspx

1-10. (canceled)
 11. A method of manufacturing a product from abio-based and biodegradable thermoplastic cellulose material comprising:decreasing a molar mass of a raw cellulose material via hydrolysis,excluding total hydrolysis, to generate a hydrolyzed molar masscontrolled cellulose, wherein the hydrolysis provides the hydrolyzedmolar mass controlled cellulose with an average molecular mass of from30 to 300 kD; performing a long chain fatty acid modification on thehydrolyzed molar mass controlled cellulose to produce the bio-based andbiodegradable thermoplastic cellulose material; and forming the productfrom the bio-based and biodegradable thermoplastic cellulose material.12. The method of claim 11, wherein the forming is done by a memberselected from the group consisting of molding, extruding, andthree-dimensional printing.
 13. The method of claim 11, wherein theforming is done in the absence of an external plasticizer.
 14. Themethod of claim 11, wherein the product is in the form of granules. 15.The method of claim 11, wherein the bio-based and biodegradablethermoplastic cellulose material is reprocessable.
 16. The method ofclaim 11, wherein the forming comprises molding or extruding theproduct, and wherein a process temperature for the forming is from 110°to 150° C.
 17. The method of claim 1, wherein the bio-based andbiodegradable thermoplastic cellulose material is compostable and/orrecyclable.
 18. The method of claim 11, wherein the bio-based andbiodegradable thermoplastic cellulose material comprises a celluloseester or ether having a chain length having between 6 and 30 carbonatoms and a degree of substitution (DS) of from 0.7 to
 3. 19. The methodof claim 11, wherein the hydrolysis reduces an average molecular mass ofthe hydrolyzed molar mass controlled cellulose by 40-85% relative to theraw cellulose material.
 20. The method of claim 11, wherein thehydrolysis is done by a member selected from the group consisting ofenzymatic treatment, ozone treatment, hydrogen peroxide treatment, andalkaline treatment.
 21. The method of claim 11, wherein the long chainfatty acid modification of the hydrolyzed molar mass controlledcellulose comprises a member selected from the group consisting ofesterification, etherification, and hydroxyalkylation.
 22. The method ofclaim 11, wherein the long chain fatty acid modification comprisesheterogeneous or homogeneous esterification of the hydrolyzed molar masscontrolled cellulose.